KR101434112B1 - Multi-purpose water-solube metalworking fluids for metal surface treatment before painting and method thereof - Google Patents

Abstract

The present invention relates to a composition solution. Elements of the composition have a lubricant effect, a cooling effect, cutting chip generating and eliminating properties, and rust-resistant properties, which are properties unique to water-soluble cutting oil. The composition solution includes at least one metal ion of tungsten, molybdenum, silicon, magnesium, vanadium, zirconium, titanium, and hafnium which are eco-friendly and have excellent durability, corrosion resistance, and heat resistance. The composition is produced by mixing and reacting fluoride as an etching agent for a metal surface, a silane coupling hydrolyzate enhancing adhesiveness, and copper ions as metal catalysts. The composition prevents formation of heavy metal sludge, formed in an existing pretreatment process; phosphate, factors for eutrophication of river and water streams, is not used for the composition solution. Therefore, the composition solution is eco-friendly.

Description

TECHNICAL FIELD [0001] The present invention relates to a metal-surface-treated composite water-soluble cutting oil and a pretreatment method thereof. [0002] MULTI-PURPOSE WATER-SOLUBE METALWORKING FLUIDS FOR METAL SURFACE TREATMENT [

Cutting oil used in machine tools is used for cutting and grinding of metals. It is generally divided into solulbe / inolulbe and semisynthetic / synthetic. The main ingredient is base oil, synthetic oil does not contain base oil) and a variety of additives. It is composed of water, stabilizer, antifoaming agent, antiseptic, antiseptic, surfactant, alkaline agent, fatty acid, inorganic Salts, synthetic esters, and minerals.
The water-soluble cutting oil in the cutting oil is classified into a transparent and translucent soluble type in which the emulsion type and the dilution solution in which the main component is diluted according to the content of the mineral oil and the surfactant are opaque and the appearance is opaque. The processing conditions of the machine tool, And cooling-action, friction-lubrication characteristics of cutting oil according to machining type (inner broaching, pipe tapping and threading, outer surface broaching and grinding, reaming, drilling, boring, hobbing, milling, turning, It is the quality of the product to maintain the uniform tooth shape and dimension required by the product by streamlining the processing, improving the precision and improving the tool life by the action of suppression and control of constituent wire, anti-corrosive action, And improvement of productivity. The solution composition of the present invention relates to a water-soluble cutting oil of the emulsion type among the emulsion type, the soluble type and the chemical (syngetic) type.
The metal material machined by machine tool CNC (Computerized Numerical Control), etc., is suitable for final product characteristics after finishing the work. It is suitable for the heat treatment process, rust prevention or user's use, It can not be applied and it needs to be painted. For painting, 12 to 14 pre-treatment steps (zinc phosphate salt coating, chromate etc.) and paint treatment are applied to the product.
In order to paint the machined metal material as described above, a metal coating salt is formed on the machined surface by a separate complicated pretreatment process, but when the metal composition is machined, when the composition solution of the present invention is used, At the same time, since an environmentally friendly coating metal salt is formed, a metal surface for coating can be provided only by a degreasing process and a water washing process without a chemical conversion coating process in a pretreatment process. In order to shorten the process and to provide convenience, an etching agent, a metal reaction accelerator (hereinafter, referred to as " metal salt ") is preferably added to form a composite metal silane film salt crystal , Metal film salt, adhesion promoter of metal film salt, and the like, and appropriately mixed and reacted with the solution of the present invention as a water-soluble cutting oil of an emulsion type of a machine tool, 3 and 4, which are 1214 processes after conventional metal work, can be obtained by cutting only the shortened process of Fig. 5 by forming a metal coating salt in addition to the characteristics of lubrication and cooling, lubrication and elimination of cutting chips, Is a new emulsion type water-soluble complex cutting oil which can be used for coating a metal surface, No deoxidation during processing and no harmful heavy metals and metal salt sludge generated during coating process. Workers do not contact with harmful heavy metals, ensuring clean workplace excluding environmentally harmful metals and shortening the number of processing steps. It has the effect of reducing operating costs, reducing the amount of carbon dioxide generated, and reducing the initial investment cost of pretreatment and painting equipment.

실란의 가수분해물과 금속이온의 반응 형성물

금속표면에서 실란의 가수분해물과 금속이온의 복합 Complex 형성

상기 R은 페인트와 결합됨
상기와 같은 금속염피막이 소재금속에 석출시 인산아연피막염의 입자크기는 1~15㎛, 크로메이트 0.15~0.25㎛이나, 발명조성물용액으로 처리된 피막입자크기는 70㎛ 이하의 박막의 나노 결정성입자로 소지 금속표면에 석출, 형성, 밀착되어 기존의 인산아연염피막이나 크로메이트 처리 제품 대비 내식성과 밀착성, 내구성, 내열성이 향상된 도장하지용 금속피막염을 제공한다.Conventional metal pretreatment methods for metal surfaces after surface treatment of metal materials include zinc phosphate salt coating of iron material and chromate treatment applied to non-ferrous metals such as aluminum are typical pretreatment for improving corrosion resistance, adhesion and durability of painted products And the number of the process steps required 12 to 14 processes as shown in FIG. 3 and FIG.
The major components of zinc phosphate coatings are phosphoric acid, nitric acid, fluorine compounds, zinc, nickel, manganese, etc. Most of them produce heavy metal sludge and used the main cause of environmental pollution. Chromate treatment used for surface treatment of nonferrous metal treatment has been causing environmental pollution by generating chromium (trivalent, hexavalent chromium) and its metal salts, which are more toxic than heavy metals (such as nickel) generated in zinc phosphating baths.
In addition, the above two typical surface treatment processes are exposed to heavy metals in the initial facility investment cost, maintenance cost and worker harmful environment, and the generated wastewater contains substances that cause river and environmental pollution, A more efficient and environmentally friendly new metal film salt composition and a simpler treatment process and a more environmentally friendly and inexpensive alternative method or novel chemical composition were required.
In order to solve such problems, the solution composition of the present invention is characterized in that the composition of the above-mentioned emulsion type water-soluble cutting oil and the environmentally friendly metals such as tungsten, molybdenum, silicon, magnesium, vanadium, zirconium, titanium, hafnium, The use of a solution prepared by mixing and reacting these strong environmentally friendly metal salts and adjusted to the appropriate conditions as an emulsion type water-soluble cutting oil in a metal machining process can maintain the function of a cutting oil during the machining of a metal material, As the local hydrogen ion concentration index (pH) of the contact interface is raised by etching, at least one of the environmentally friendly metals forms a film material of a fluorine compound, a hydroxide, and an insoluble compound in the form of an oxide to precipitate on the metal surface, Silane coupling hydrolyzate improves adhesion and corrosion resistance Such, the chemical reactions invention composition solution to be precipitated in the steel sheet surface is estimated to be:
▶ Conventional Metal Film Formation Mechanism: Zinc Phosphate Coating, Chromium Coating
▷ Zinc Phosphate Formation Mechanism - Material: CR (SPCC)
Fe + 2H ₃ PO ₄ ------- Fe (H ₂ PO ₄ ) ₂ + H ₂ ↑
(Metal) (acid in coating solution) |
| (O: oxygen supply from accelerator)
| ---- → FePO ₄ + H ₃ PO ₄ + 1 / 2H ₂ O
Sludge (including nickel, manganese and zinc sludge)
3Zn (H ₂ PO ₄ ) ₂ ------- 3Zn ₃ (H ₂ PO ₄ ) ₂ .H ₂ O + 4H ₃ PO ₄
(Coating solution) Zinc phosphate salt coating (Hopeite)
Fe + 2Zn (H ₂ PO ₄ ) ₂ --- 3Zn ₂ Fe (H ₂ PO ₄ ) ₂ .4H ₂ O + 2H ₃ PO ₄ + H ₂ O
Phosphophyllite (Phosphophyllite)
▷ Mechanism of formation of passive film - Material: AL
^{_{2AL + Cr 2 O 7 -2 +}} 14H + → 2AL +3 + 2Cr +3 + 7H 2 O
_{Cr (OH) 3 + CrO 3} → Cr (OH) 3. Cr (OH). CrO ₄ + H ₂ O
Chromium coating
The film-forming mechanism of the inventive composition (in the alkaline part of the cutting oil)
H2SiF ₆ + 2NaOH + H2O Na2SiF _{6
Na2SiF 6 + 4NaOH 6NaF + SiO +} 2H2O

H2ZrF ₆ + 2NaOH + H2O Na2ZrF6
_{Na2ZrF 6 + 4NaOH 6NaF + ZrO +} 2 H2O

Reaction Mechanism of Metal and Silane Hydrolyzate in Emulsion-Type Water-Soluble Coolant
Hydrolysis of silane, condensation reaction (hydrolyzate of silane)

Reaction Formation of Hydrolyzate of Silane and Metal Ion

Complex Complex Formation of Silicon Hydrolyzate and Metal Ion on Metal Surface

The R is combined with the paint.
When the metal salt film is deposited on the base metal, the zinc phosphate film salt has a particle size of 1 to 15 탆 and a chromate of 0.15 to 0.25 탆, but the film particle size treated with the inventive composition solution is a nanocrystalline thin film having a size of 70 탆 or less The present invention provides a metallic coating salt for coating, which is improved in corrosion resistance, adhesion, durability, and heat resistance compared to conventional zinc phosphate coatings or chromate treated products by precipitation, formation, and adhesion to the surface of base metal.

Metal materials requiring painting are subjected to a pretreatment and painting process for chemical coating after metal cutting using water-soluble cutting oil of emulsion type in machine tool for tooth shape and size.
Conventional pretreatment process is a pretreatment with a chemical conversion coating agent (zinc phosphate coating agent, chromium film coating agent) prepared by dissolving harmful heavy metals (nickel, chromium, zinc, manganese, etc.) in human body into phosphoric acid, nitric acid, The representative processes are "Tanse-preliminary degreasing-main degreasing-rinsing-rinsing-surface treatment-rusting coating-rinsing-rinsing-rinsing-pure rinsing", and two to four processes are added depending on the material characteristics. Each process can be classified into two types according to the given treatment conditions: "Blessing, degreasing process - maintaining appropriate temperature, alkalinity, oil content", "flushing - maintenance of contamination", "surface adjustment - pH, maintenance of alkali" (Metal content should be checked once a month) should be checked every 2 to 4 hours, and also for the coating of aluminum wheels During the pre-treatment process, as shown in Fig. 9, The metal surface is contaminated with the metal surface, and the failure cost is increased. In addition, the operation conditions of the utility of each process for operating the metal surface are checked and adjusted at various times to provide a metal surface for painting, Should add a pickling (etching) process to remove oxide on the surface of the workpiece.
In addition, the accelerator decomposition gas (nitrate gas) generated in the zinc phosphate film is rusted when contacted with the work metal, and corrosion resistance after painting is lowered. Since the chromium vapor generated in the chromium process is very toxic to the human body, Of the exhaust system.
The composition solution of the present invention was developed in order to overcome the limitation of an emulsion type water-soluble cutting oil used in conventional metal surface machining and to shorten the pre-processing step in a post-process. In addition, Pre-degreasing-main degreasing-rinse-pure three-dry-painting "process which is shortened by simultaneously forming a metal film salt on the metal surface The formed metal film salt can reduce the operation cost by shortening the process time and the effect of extending the work waiting time from the external atmospheric condition before coating, and it is possible to reduce the operation cost of the heavy metal and its salt harmful to the human body, The present invention relates to a composite water-soluble cutting oil composition for an emulsion type metal surface treatment capable of carrying out an environmentally friendly work without gas generation, There is a main objective for.

The metal material required to be painted was separated and operated in a machining process by a machine tool and a process of forming a metal film salt in a pretreatment process. However, the composition solution of the present invention is a conventional emulsion type water- It is a composition prepared by appropriately mixing and reacting "mineral oil, lower fatty acid, higher fatty acid, alkali agent and preservative, surfactant, antifoaming agent, antiseptic agent and additive" which is a constituent of the cutting oil, and more specifically, polyoxy 15 to 40 wt / v% of a polyoxyethylene alkyl ether, 5 to 15 wt / v% of a triethanolamine, 1,2-Benzisothiazolin-3- One to 15 wt / v% of petroleum hydrotreated light paraffinic, 15 to 25 wt / v% of ethanolamine, 2 to 5 wt / v% of sebacic acid, 5 to 15 wt / v% of ricinoleic acid, triethanolpropane triole 3 to 5 wt / v% of trimethylolpropanetrioleate, 1 to 3 wt / v% of polyethylene glycol monobutylether, 1 to 3 wt / v% of dicarboxylic acid, polyoxypropylene glycol monoalkyl ether Polyoxypropylene glycol monoalkyl ether) and 10 to 600 ppm of at least one water-soluble metal ion selected from tungsten, molybdenum, silicon, magnesium, vanadium, zirconium, titanium and hafnium which are eco- / v% It is a composition solution diluted with an appropriate amount of pure water (Di-ion water) after mixing and reacting under proper conditions to contain silane hydrolyzate, hydrofluoric acid salt, metal copper salt and so on. (PH) of 8.5 to 9.5 when diluted to a cutting oil content of 8%, 10 to 100 ppm of free fluorine, 10 to 30 ppm of copper ion, 100 to 600 ppm of film metal content, and adjusted to a solution temperature of 5 ↑ ≪ / RTI > When supplied to the metal surface, a suitable environmentally friendly complex metal salt crystal silane coating need not be formed for a while maintaining the characteristic features of the water-soluble cutting oil in the emulsion coating on a metal material surface. In addition, each component can be appropriately added and mixed to form a composite metal silane film salt crystal, and a substitute material can be used.
The hard paraffin oil, which is a main component of the conventional emulsion type water-soluble cutting oil, is a lubricant medium which is dispersed and emulsified by the added surfactant (polyoxyethylene alkyl ether) to form a stable solid film lubrication on the metal surface during the machining operation, Fatty acids such as ricinoleic acid and triethanolpropane trioleate are used in combination for improving the surface roughness and viscosity of the surface. The polyoxypropylene glycol monoalkyl ether is an anti-foaming agent, which is used in an incombustible type non-silicone type), it is possible to control the clearing occurring on the paint surface in the drying furnace after coating. Neutralizing, anti-oxidation, saponification reaction of the fatty acid and the hydrogen ion index (pH) of the silane hydrolyzate and composition solution And stabilizing, and silicon, zirconium or the like dissolved in a metal salt in the composition The pH of the composition should be maintained at 8.5 to 9.5. When the pH is 8.5, the emulsion type of lubrication and cutting effect should be maintained. If the pH is 9.5, the metal ions are precipitated and the film is not formed on the surface of the metal during the machining, and the metal film weight for copper ions , The corrosion resistance after coating is deteriorated even if a decarboxylic acid liquid and sebacic acid are contained in the composition as a rust preventive agent. The 1,2-benzisothiazoline-3-one is used as an antimicrobial agent for preventing the deterioration of the composition, and is useful for preventing deterioration of copper ion and metal fluoride salt composition solution used as an etchant .
In preparing the solution composition of the present invention, the environmentally friendly silane hydrolyzate is dissolved in an environmentally friendly metal salt, a metal fluoride salt, a copper salt, and the like, and then the pH of the solution composition is adjusted to 8.5 to 9.5 It is possible to control the precipitation of the metal salt and the side reaction with the fatty acid which is a constituent component in the composition and to stabilize the entire solution of the invention of the invention, Pretreatment process - The composite metal silane film salt crystals formed on the metal surface at the time of the coating process standby will have less external influence on the exposed metal surface compared to the conventional emulsion type water soluble cutting oil.
When a casting such as an aluminum wheel is continuously supplied to the bite or drill work (Hole), which is the contact surface of the wheel, the fluorine compound as a metal surface etching agent in the inventive solution increases the reactivity in a short time, and the environmentally- , An insoluble metal compound of an oxide type thin film is precipitated and formed on the metal surface as nano-sized crystal grains, and at the same time, the metal precipitate improves the adhesion force by the silane coupling hydrolyzate to form the metal coating salt required in the coating, In addition to the cutting oil remaining on the surface of the workpiece, the anti-rust effect is increased.
In addition, the chemical reaction occurs rapidly due to the increase in temperature due to friction at the interface between the workpiece and the metal surface. Copper, which is the etchant of the constituent components, and the metal promoter, and the hydrolyzate of the silane, During the chemical reaction, the emulsion-type cutting oil is blended so as not to be influenced by the organic compound component, and the chemical reaction proceeds also by residual heat on the surface of the workpiece after contact with the bite on the surface of the workpiece.

Conventional emulsion type water-soluble cutting oil improves the cutting tool part and tool life due to the cooling action during the operation of the machine tool, reduces friction and tool wear due to lubricating action, improves the dimensional accuracy of the machined part, (zinc phosphate salt coating, chromate etc.) in a separate facility so that the machined metal material has corrosion resistance and weatherability. In addition, A metal coating suitable for coating is formed on the surface of the metal material and then painted using paint paint. However, when the solution of the present invention is applied, Prevention of erosion from the surface of the workpiece during temporary storage before the pretreatment process is applied after using the conventional emulsion type water-soluble cutting oil It is possible to work in a shorter process (shortening of 12 to 14 processes to 7 processes) since it does not require a zinc phosphate film and a chromate film in the pretreatment process after metal cutting, and the advantage of working with heavy metal sludge (Phosphate coatings - zinc, nickel, manganese and metal salts, chromate coatings - chromium and metal salts), and the use of phosphoric acid, which is the root cause of river and river enrichment, is environmentally friendly. By eliminating the need for specialized technicians, it is possible to reduce the cost of process facility operation and wastewater treatment, reduce energy consumption, eliminate environmental pollutants, clean the workplace, reduce carbon dioxide emissions, (SPCC), aluminum (AL), as well as cutting and grinding work processes of various kinds of nonferrous metals and cast products Neunghada.
▶ Conventional zinc phosphate salt coating process (12 processes)
Tanse - Pre-degreasing - Bone degreasing - Washing - Washing - Surface adjustment - Zinc phosphate coating -
Washing - Washing - Pure Three - Drying - Liquid Paint
- Drying - Powder coating
- Electro deposition
▶ Conventional chromate coating process (14 processes)
Sanse - Preliminary degreasing - Main degreasing - Washing - Washing - Sansing (etching) - Washing - Washing - Passing
- Washing - Washing - Pure water - Drying - Liquid paint
- Drying - Powder coating
- Electro deposition
▷ Process of applying the invention composition (7 processes)
Tanse - Pre-degreasing - Bone degreasing - Washing - Pure three-drying - Liquid paint
- Drying - Powder coating
- Electro deposition

Figure 1 shows an overall schematic diagram of the manufacturing process of an aluminum wheel
Figure 2 is a schematic diagram of a pre-
3 is a schematic view showing a conventional aluminum wheel pre-treatment process (chromate treatment)
4 is a schematic view showing a conventional zinc iron phosphate pretreatment process.
FIG. 5 is a schematic view showing the shortening process of the pretreatment process according to the present invention
FIG. 6 is a photograph of AFM photograph of aluminum wheel material after treatment of the invention solution
FIG. 7 is a photograph of AFM photograph of iron material after the invention solution treatment
8 is a SEM (x1000 magnification) photograph of a conventional zinc iron phosphate coating
Fig. 9 is a photograph of a surface contamination SEM (x5O, x200)

{ 표 2 } 크로메이트 처리 및 도장방법

{ 표 3 } 인산아연염피막의 요구품질 및 시험방법

[ 표 4 ] 크로메이트피막(알루미늄휠)의 요구품질 및 시험방법

{ 표 5 } 전처리 피막 후 금속표면의 피막부착량 측정

{ 실시 예 }
▶ 금속표면 가공용 복합 수용성 절삭유(에멀젼타입)
발명용액조성물을 농도를 8％가 되도록 희석하여 대표도 도 1 피삭공정인 "CNC ＆ P.C.D Valve hole machining"에서 냉연봉강(SPCC)과 알루미늄휠등 2종류를 피삭가공하여, 대표도 도 5의 "발명조성물용액 처리 후 전처리 공정" 처리 후 전착도장(실시 예1, 예2, 예3)과 분체, 액상소부도장(실시 예4 ∼예113)하여 실시 예의 시료로 사용하였으며 금속표면의 피막부착량은 { 표 5 }와 같았다.
▶ 적용페인트와 각 도장 시료의 관련 규격과 시험항목, 평가 방법은 비교 예와 동일하다DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings.
The composition solution of the present invention has the effects of cooling, lubrication, and rust prevention of the water-soluble cutting oil of the machined surface of the metal surface with CNC and the detailed constituent components for forming the composite metal silane film salt crystal on the metal surface during machining, , 35.0 wt / v% of polyoxyethylene alkyl ether as an active agent, 5.0 wt / v% of triethanolamine, and 1,2-Benzisothiazolin-3- One, 1.0 wt / v%, 15.0 wt / v% petroleum hydrotreated light paraffinic, 1.5 wt / v ethanolamine, 2.0 wt% sebacic acid, , 15.0wt / v% of Ricinoleic acid, 3.0wt / v% of Trimethylolpropanetrioleate, 1.0wt / v% of Polyethyleneglycol monobutyl ether, Dicarboxylic acid solution of Dicarboxylic acid acid, 1.5 wt / v%, polyoxypropylene glycol monoalkyl ether lkyl Ether) containing 10 to 600 ppm of at least one water-soluble metal ion selected from tungsten, molybdenum, silicon, magnesium, vanadium, zirconium, titanium and hafnium in an appropriate amount of pure environmentally friendly metal, 10 to 100 ppm of fluorine free fluorine to finely etch the surface of the silane hydrolyzate and the metal surface to promote the reaction, and 10 to 30 ppm of copper ions to promote the reaction and increase the metal film salt weight. ) And a composition solution adjusted to have a temperature of the composition of 5 or more and a hydrogen ion index (pH) of 8.5 to 9.5 is added to the surface of the metal to be machined so as to maintain the characteristics and function of the emulsion type water- Suitable environmentally friendly composite metal silane film salt crystals are formed on the metal surface of the material necessary for coating. In the above description, each component should be appropriately reacted or added to maintain the function of emulsion type water-soluble cutting oil and metal film salt formation, and a substitute material may be used
When the solution of the present invention is continuously supplied to the cutting tool portion during the machining of metal, nonferrous metal or casting materials, etc., the etchant in the inventive solution increases the reactivity within a short time due to the friction heat caused by the workpiece, Or a metal-insoluble compound of a thin film of a hydroxide and an oxide form is formed and precipitated on the surface of the processed metal while the metal precipitate is enhanced in adhesion by the silane coupling hydrolyzate to form a metal film To form a salt.
Alcoholic amines are substances for neutralization and saponification reaction of fatty acids and for controlling the pH of the inventions, and include ethanolamine and triethanolamine. Propanolamine, dimethyl ethanol Dimethylethanolamine, N-methylethanolamine and the like can be similarly used, and the supply source thereof is not particularly limited.
Dicarboxylic acid is used for the purpose of preventing corrosion after machining or after machining, but the source for this is not particularly limited.
Polyoxyethylene alkylphenyl ether is a surfactant. It is used to maintain uniformity of composition solution and prevent re-adhesion of contaminants by penetration, emulsification and dispersing action of the invention composition solution and metal surface. However, in case of excessive use, It is necessary to use as small a quantity as possible, and the supply source for this is not particularly limited.
A small amount of 1,2-benzisothiazolin-3-one can be added as an additive for preventing the deterioration of the composition solution and preventing the growth of fungi and bacteria. It is a drug for preventing the deterioration of the composition, and the source of the drug is not particularly limited.
The use of hard petroleum hydrotreated light paraffinic oil as an extreme pressure additive is not specifically limited.
Ricinoleic acid is used as a lubricant for the machined surface and as a component of the release agent, but the source for the lubricant is not particularly limited.
Sebacic acid is used as an auxiliary rust inhibitor for the workpiece, but the source for this is not limited
Trimethylolpropanetrioleate is used for improving the roughness of the surface of the machined metal and for controlling the viscosity of the composition, but the supply source thereof is not particularly limited.
Polyethyleneglycol monobutyl ether is used for the purpose of improving the mixing and dispersing properties with fatty acids in the constituent components, but the supply source thereof is not particularly limited.
The antifoaming agent used for excessive bubble removal during work is selected so that excessive bubbles are not generated during the work. Especially, it is remained on the metal surface during the machining process and the water-soluble silicone causes clearing (Water-soluble non-silicone type such as polyoxypropylene glycol monoalkyl ether) should be used, and the supply source thereof is not particularly limited.
Metal ion content of tungsten, molybdenum, silicon, magnesium, vanadium, zirconium, titanium and hafnium, which are eco-friendly film metals, can be used up to 100 ~ 5,000ppm for metal film salt formation. When the metal content is less than 5,000 ppm, the precipitation time of the metal salt is shortened, but the aging of the solution is accelerated. In addition, since the loss of high-concentration metal ions is increased during the post-process shift of the workpiece, The content is preferably 100 to 600 ppm, and the metal ion can be used by using an inorganic salt or an organic compound such as a carbonate, a fluoride salt, an ammonium salt, a nitrate salt or the like of the metal or by appropriately reacting it.
Silane hydrolyzate was prepared by adding pure water to aminosilane, vinylsilane and epoxy silane such as 3-Aminopropylmethyldiethoxysilane, Vinyl (2-Methoxyethoxy) silane and 3-Glycidoxypropyltrimethoxysilane to increase the adhesion of metal film salt and improve lubricity when machining. % And the solution is kept at pH 4 (hydrogen ion index) while stirring at 40 to 45, and a weak acid such as acetic acid is added and kept for 1 hour to prepare a silane hydrolyzate. The silane hydrolyzate is precipitated in an alkali solution or an acidic solution The metal coating salt which is not decomposed and deposited on the surface of the steel sheet must be selected, reacted and made to increase the adhesion to the paint, and the supply source thereof is not particularly limited.
The free fluorine used as an etchant on the surface of the workpiece dissolves the metal surface within a short time on the surface of the workpiece so that the metal film salt composition is in direct contact with the surface of the workpiece, The coating salt reacts with the silane hydrolyzate to precipitate and form insoluble fluorine compounds, hydroxides, oxide forms or hydrolyzates of the composite metal silane on the metal surface. When the amount of free fluorine ions is less than 10 ppm, surface etching of the metal or non-ferrous metal is not sufficiently formed, so that the proportion of the metal salt film deposited on the surface of the base metal is low and the coating corrosion resistance is lowered. It is preferable that the free fluorine ion is 10 to 100 ppm in order for the effective etching to be performed because the etching is excessive and the appearance damage of the base metal is increased and the metal ion content of the etched metal is increased to cause economic loss due to rapid aging of the working solution. The source of free fluorine may be inorganic salts or organic compounds such as carbonates, fluorides, ammonium salts and nitrates, but is not particularly limited.
Copper used as an accelerator of metal film salt accelerates the metal coating salt and increases the coating thickness of the workpiece. If the copper ion content is less than 10 ppm, the coating amount on the surface of the metal or non-metal is insufficient, And if it is 30 ppm or more, copper partially precipitates on the surface of the metal to discolor the surface of the metal, so that the copper ion content is preferably 10 to 30 ppm. The source of copper ions may be inorganic salts or organic compounds such as carbonates, fluorides, ammonium salts and nitrates of metals, but is not particularly limited.
The pH of the hydrogen ion may be appropriately selected from organic compounds or mixtures such as amine alcohols and metal inorganic salts such as carbonates, fluorides, ammonium salts and nitrates for the purpose of storage stability of the working solution and corrosion of the workpiece The pH of the solution is preferably adjusted to 8.5 to 9.5, more specifically, the solution may be deteriorated by fungi and bacteria in the solution composition at pH 8.5. When the pH is 9.5, And may be partially corroded or discolored on the surface of the metal during the corrosion of the surface of the non-ferrous metal or storage after processing. Therefore, it is preferable to use it within the pH range of 8.5 to 9.5.
Since each constituent material affects the coating quality, the working solution should be selected and compounded so that the contaminants do not adhere to the surface of the workpiece, flocculate, do not generate metal stone gravel or sludge, Shall have a function of water-soluble cutting oil of emulsion type and a metal ion content of 100 to 600ppm, a pH of 8.5 to 9.5, a copper ion of 10 to 30ppm and a free fluorine content of 10 to 100ppm.
When the components of the composition of the present invention are mixed and stirred while excluding the silane hydrolyzate and the eco-friendly metal salt (such as zirconium salt), the pH of the solution is adjusted to 9 with an alkaline component such as triethanolamine, There is no side reaction during the mixing. Separately, the silanol hydrolyzate and the eco-friendly metal salt (zirconium etc.) are stirred and dissolved, and then the two solutions are mixed while stirring. The triethanolamine is diluted with pure water so that the hydrogen ion index of the solution becomes pH 9 And then the mixture is added in small amounts. The composition solution should be free of chemical reaction or precipitate by each constituent material, and chemical reaction occurs only when it is contacted with metal or nonferrous metal to form a composite metal silane film salt crystal on the metal surface
The surface treatment method using the inventive solution composition described above will be described in more detail.
In the "CNC PCD Valve hole machining", which is a metal working process in the aluminum wheel manufacturing process, the solution temperature was maintained at 5 or more by using the composition of the present invention. Fig. 5: The water-soluble cutting oil content of the emulsion type in the inventive composition was measured with a BRIX densitometer, the concentration was corrected, and the metal content in the working solution was analyzed using "ICP " The adhesion amount of the metal film on the surface of the material was measured by FRX.
The following experiment was carried out in order to examine the technical effects of the metal surface treatment solution composition for surface treatment using an aqueous emulsion-type composite water-soluble cutting oil for surface treatment of the present invention and its surface treatment method.
Comparative Example
Pretreatment agent
As a sample of the comparative example of the composition solution of the present invention, two types of ordinary cold-rolled steel (SPCC) and aluminum wheel were processed at a drive shaft rotation speed of 2,000 rpm using a conventional emulsion type water-soluble cutting oil (BRIX concentration 8% The zinc phosphate coating (electrodeposition coating) of the domestic automobile coating line and the chromate coating treatment of the table 2 were subjected to electrodeposition coating (Comparative Example 1), powder coating, liquid baking coating (Comparative Example 2-general painted product, and Comparative Example 3-D / C painted product).
The relevant standards, test items and evaluation methods of each coating sample were tested in accordance with "KS D ISO 3520, Test method for Cohesion of Coatings for KS M ISO 2409 Coatings" And Table 3 and Table 4 were applied. The coating amount of the metal surface was as shown in Table 5.
Apply paint
. Electrodeposition coating: The electrodeposition coating (NV: 19 wt / v%) used in the domestic automotive parts coating line was used as the applied coating after zinc phosphate coating salt treatment of Comparative Example 1.
. Liquid paint, Powder coating: The same product used in domestic automotive aluminum wheel coating line (treated in aluminum wheel process)

{Table 1} Zinc phosphate coating and electrodeposition coating method

{Table 2} Chromate treatment and coating method

{Table 3} Required quality and test method of zinc phosphate salt coating

[Table 4] Required quality and test method of the chromate film (aluminum wheel)

{Table 5} Measurement of film adhesion on metal surface after pretreatment film

{Example}
▶ Complex water-soluble cutting oil for metal surface treatment (emulsion type)
Representative Fig. 1 shows that the inventive solution composition was diluted so as to have a concentration of 8%. In the CNC & PCD Valve hole machining, which is a machining process, two types of machining were carried out: cold rolling steel (SPCC) (Example 1, Example 2, Example 3) and powder and liquid phase baking (Examples 4 to 113) after the pretreatment process of the inventive composition solution was used as a sample of the example, {Table 5}.
▶ The relevant specifications, test items and evaluation methods of applied paint and each paint sample are the same as the comparative example

{ 표 6-2 } 피삭금속의 전처리 및 액상 소부도장공정(총 7개 공정)

The cold-rolled steel bar was subjected to the conditions of application of the inventive composition solution in the following conditions of "CNC inventive composition processing conditions" of {Table 6-1} below: hydrogen ion index (pH) of 8.5, metal ion content of 100 ppm, free fluorine of 10 ppm and copper ion of 10 ppm The solution was applied to the workpiece machining process by adjusting the rotation speed of the CNC drive shaft to 1,500 rpm and then subjected to the pretreatment and the coating of the {Table 6-2} process, and the same specifications, test items and methods as those of the above- Respectively.
{Table 6} Conditions for treating solution of the invention composition, pretreatment and coating process
{Table 6-1} Solution conditions of the invention composition - Emulsion type

{Table 6-2} Pre-treatment of machined metal and liquid-phase baking process (total 7 processes)

Hydrogen ion index (pH) of the inventive composition solution 9.0 A sample was treated in the same manner as in Example 1, except that a solution containing 200 ppm of a metal content, 20 ppm of free fluorine, and 10 ppm of copper ion was changed to a rotation speed of the CNC drive shaft at 2,000 rpm.

Hydrogen ion index (pH) of the inventive composition solution 9.5 A sample was treated in the same manner as in Example 1 except that the solution containing a metal content of 300 ppm and a free fluorine content of 40 ppm was changed to a rotation speed of the CNC drive shaft at 2,500 rpm.

An aluminum wheel was immersed in a solution of the inventive solution in a solution condition of pH 8.5, metal content of 100 ppm, free fluorine of 10 ppm and copper ion of 10 ppm in CNC After the rotation speed of the drive shaft was adjusted to 1,500 rpm, it was applied to the material machining process. The aluminum wheel was pretreated, powdered after drying, and baked with liquid paint (except electrodeposition coating) The items and methods were applied in the same manner as in the comparative example.

The sample was treated in the same manner as in Example 4 except that the hydrogen ion index (pH) of the inventive solution was changed to 9.0.

The sample was treated in the same manner as in Example 4 except that the pH of the inventive solution was changed to 9.5.

The sample was treated in the same manner as in Example 4 except that the metal content of the inventive solution was changed to 200 ppm.

The sample was treated in the same manner as in Example 4 except that the metal content of the inventive solution was changed to 300 ppm.

The sample was treated in the same manner as in Example 4 except that the metal content of the inventive solution was changed to 400 ppm.

The sample was treated in the same manner as in Example 4 except that the metal content of the inventive solution was changed to 500 ppm.

The sample was treated in the same manner as in Example 4 except that the metal content of the inventive solution was changed to 600 ppm.

The sample was treated in the same manner as in Example 5 except that the metal content of the inventive solution was changed to 200 ppm.

The sample was treated in the same manner as in Example 5 except that the metal content of the inventive solution was changed to 300 ppm.

The sample was treated in the same manner as in Example 5 except that the metal content of the inventive solution was changed to 400 ppm.

The sample was treated in the same manner as in Example 5 except that the metal content of the inventive solution was changed to 500 ppm.

The specimen was treated in the same manner as in Example 5 except that the metal content of the inventive solution was changed to 600 ppm.

A sample was treated in the same manner as in Example 6 except that the metal content of the inventive solution was changed to 200 ppm.

The sample was treated in the same manner as in Example 6 except that the metal content of the inventive solution was changed to 300 ppm.

A sample was treated in the same manner as in Example 6 except that the metal content of the inventive solution was changed to 400 ppm.

The sample was treated in the same manner as in Example 6 except that the metal content of the inventive solution was changed to 500 ppm.

The specimen was treated in the same manner as in Example 6 except that the metal content of the inventive solution was changed to 600 ppm.

The sample was treated in the same manner as in Example 4 except that the amount of free fluorine in the inventive solution was changed to 20 ppm.

A sample was treated in the same manner as in Example 4 except that the free fluorine content of the inventive solution was changed to 40 ppm.

A sample was treated in the same manner as in Example 4 except that the amount of free fluorine in the inventive solution was changed to 60 ppm.

A sample was treated in the same manner as in Example 4 except that the amount of free fluorine in the inventive solution was changed to 80 ppm.

The sample was treated in the same manner as in Example 4 except that the free fluorine content of the inventive solution was changed to 100 ppm.

The sample was treated in the same manner as in Example 4 except that the amount of free fluorine in the inventive solution was changed to 150 ppm.

The sample was treated in the same manner as in Example 5 except that the amount of free fluorine in the inventive solution was changed to 20 ppm.

Samples were treated in the same manner as in Example 5 except that free fluorine in the inventive solution was changed to 40 ppm.

The sample was treated in the same manner as in Example 5 except that the free fluorine content of the inventive solution was changed to 60 ppm.

The sample was treated in the same manner as in Example 5 except that the free fluorine content of the inventive solution was changed to 80 ppm.

Samples were treated in the same manner as in Example 5 except that free fluorine in the inventive solution was changed to 100 ppm.

The sample was treated in the same manner as in Example 5 except that the amount of free fluorine in the inventive solution was changed to 150 ppm.

The sample was treated in the same manner as in Example 6 except that the amount of free fluorine in the inventive solution was changed to 20 ppm.

Samples were treated in the same manner as in Example 6 except that the free fluorine content of the inventive solution was changed to 40 ppm.

Samples were treated in the same manner as in Example 6 except that the free fluorine content of the inventive solution was changed to 60 ppm.

The sample was treated in the same manner as in Example 6 except that the amount of free fluorine in the inventive solution was changed to 80 ppm.

The sample was treated in the same manner as in Example 6 except that the amount of free fluorine in the inventive solution was changed to 100 ppm.

The sample was treated in the same manner as in Example 6 except that the amount of free fluorine in the inventive solution was changed to 150 ppm.

A sample was treated in the same manner as in Example 4 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 7 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 8 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 9 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 10 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 11 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 12 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 13 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 14 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 15 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 16 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 17 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 18 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 19 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 20 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 21 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 22 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 23 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 24 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 25 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 26 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 27 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 28 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 29 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 30 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 31 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 32 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 33 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 34 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 35 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

A sample was treated in the same manner as in Example 36 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 37 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 38 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 39 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm.

The sample was treated in the same manner as in Example 4 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 7 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 8 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 9 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 10 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 11 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 12 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 13 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 14 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 15 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 16 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 17 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 18 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 19 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 20 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 21 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 22 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 23 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 24 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 25 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 26 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 27 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 28 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 29 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 30 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 31 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 32 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 33 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 34 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 35 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 36 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 37 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

The sample was treated in the same manner as in Example 38 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 39 except that the rotation speed of the CNC drive shaft was changed to 2,500 rpm.

A sample was treated in the same manner as in Example 1 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm and 20 ppm of copper ion.

A sample was treated in the same manner as in Example 1 except that the rotational speed of the CNC drive shaft was changed to 2,000 rpm and 30 ppm of copper ions.

The sample was treated in the same manner as in Example 1 except that the rotation speed of the CNC drive shaft was changed to 2,000 rpm and 40 ppm of copper ion.

The surface of the aluminum wheel was polished at a rotational speed of 2,000 rpm using a conventional emulsion type water-soluble cutting oil. The surface of the aluminum wheel was polished (Table 6-1). The pH of the inventive composition was 8.5, the metal ion content was 200 ppm, 10 ppm of copper ions and 10 ppm of copper ions were stirred at 50 rpm at a temperature of 40 ° C for 3 minutes to prepare a sample for pretreatment of the working metal (Table 6-2), a liquid baking step (7 steps in total) And used as a test sample.

A sample was treated in the same manner as in Example 111 except that the metal ion content was changed to 300 ppm.

종래의 인산아연피막염과 크로메이트피막 처리된 비교 예1~예3은 이미 상용화된 방법으로 국내 도장 관련업계에서 요구하는 대부분의 시험 항목을 만족한다. 그러나 철 소재(CR)에서 염수분무성 시험시간을 종래의 일반적인 기준인 500~720시간을 800시간으로, 알루미늄소재(AL)의 CASS 시험시간을 120~168시간에서 200시간으로 연장하여 시험시 비교 예1, 예2, 예3에서 각각 시험전 도장표면의 Cut 부위로부터 4mm이상의 부식이 발생하였으나 실시 예 13의 철소재(CR)과 실시 예4~110의 알루미늄소재는 비교 예 대비 모두 보다 좋은 결과를 얻을수 있었고, 내염온수 2차부착성(240시간)과 염수분무성 시험에서도 비교 예1예3 대비 실시 예1~예3과 예4~예110은 시험 후 편측 박리 정도가 양호하였고, 유리불소함량을 10~100ppm으로 처리된 시료는 외관변색이 없으나 150ppm으로 상승시킨 실시 예27, 예33, 예39, 예61, 예67, 예73, 예95, 예101, 예107의 시료는 부분적으로 과도한 표면에칭이 발생하여 피삭표면에서 약한 연갈색엷은검은색의 변색되었다.
구리이온함량조건을 변경시킨 실시예108, 예109은 양호하나 실시 예110은 표면색상이 구리색갈색으로 변색되어 외관 불량이 발생되었다.
Filliform 시험은 종래의 일반적인 시험시간인 680~1000시간을 1000시간 까지 시험 후 관찰시 비교예2, 예3과 실시 예4실시 예110 모두 양호하였고, 내염 온수 2차부착성(240시간)에서는 편측 박리정도가 비교 예 보다 양호한 결과를 얻을 수 있었으며, CNC 구동축 회전속도에 따른 도장물성 차이는 없었다.
또한 실시 예112, 예113에서 종래의 에멀젼타입의 수용성절삭유로 피삭된 알루미늄 소재를 발명조성물용액에서 침적, 교반하여 전처리, 도장처리한 제품은 염수분무성에서 480시간, CASS 120시간, Filliform 480시간까지는 양호하였으나 이 후 부식이 급속히 진행되었고, 본 발명조성물용액을 피막 대체로 시험된 예111~예113에서 금속이온함량이 높은 실시 예113~예112은 실시 예111보다 시험 후 편측 부식진행 정도가 다소 나았으며, 금속이온함량이 높을수록 CASS, Filliform, 염수분무성이 향상되는 것으로 추정되며, 본 발명용액을 사용하면 산업현장에서 본 발명용액을 종래의 에멀젼타입의 수용성절삭유를 대체하여 사용되면 친환경적작업장 운용과 신설되는 표면처리공정-도장공정설비의 비용절감과 이산화탄소발생 억제로 기존의 공정보다 향상된 경쟁력을 가질 것으로 판단된다. A sample was treated in the same manner as in Example 111 except that the metal ion content was changed to 400 ppm.
[Table 6] Test results after pre-treatment and painting

Comparative Examples 1 to 3, in which conventional zinc phosphate film salt and chromate film were treated, satisfy most of the test items required in the domestic painting industry by the already commercialized method. However, in the case of iron CR, the test time of salt water ash was extended from 500 ~ 720 hours to 800 hours and the CASS test time of aluminum material (AL) from 120 ~ 168 hours to 200 hours. Corrosion of more than 4 mm from the cut portion of the surface of the coating before test in Examples 1, 2 and 3, respectively, was observed, but the iron material (CR) of Example 13 and the aluminum material of Examples 4 to 110 had better results (240 hours) of salt water warming water and in the salt water silting test, the degree of unilateral peeling after the test was good in Examples 1 to 3 and 4 to 110 compared to Comparative Example 1, The samples treated with 10 to 100 ppm of the sample were partially washed with the sample of Example 27, Example 33, Example 39, Example 61, Example 67, Example 73, Example 95, Example 101, Excessive surface etching occurs, resulting in a weak light brown to light black discoloration on the work surface It was.
Examples 108 and 109 in which the copper ion content condition was changed were good, but in Example 110, surface color changed to brownish brown and appearance defect occurred.
In the Filliform test, the conventional test time of 680 to 1000 hours was observed up to 1000 hours, and the test results of Comparative Example 2, Example 3 and Example 4 were all good, and in the salt water warm water secondary adhesion test (240 hours) The degree of peeling was better than that of the comparative example, and there was no difference in paint properties according to the rotation speed of the CNC drive shaft.
In Examples 112 and 113, the aluminum material peened with the water-soluble cutting oil of the conventional emulsion type was immersed and stirred in the inventive composition solution and pretreated and painted, the product was washed with 480 hours of salt water, 120 hours of CASS, 480 hours of Filliform But the corrosion progressed rapidly after that. In Examples 111 to 113 in which the solution of the composition of the present invention was tested as a coating film, in Examples 113 to 112 in which the metal ion content was high, the degree of unilateral corrosion progressed somewhat And it is estimated that the higher the metal ion content, the better the CASS, Filliform, and salt water silence. If the solution of the present invention is used instead of the conventional emulsion type water-soluble cutting oil in the industrial field, Operation and new surface treatment process - Cost reduction of coating process equipment and suppression of carbon dioxide generation It is expected.

▶ Representative figure 2
▷ Conventional zinc phosphate coating process
1: Tanse 2: Degreasing 3: Degreasing
4: Washing 5: Washing 6: Surface adjustment
7: zinc phosphate coating 8, 9: waterproof 10: pure water
▷ Process after Application of Invention Composition Solution
1: Tanse 2: Invention solution 3: Invention solution
4: pure three 5: pure three

Claims (7)

In an aqueous emulsion type cutting oil used in the machining of metal or nonferrous metal surfaces, one or more of metal ions and silane hydrolyzate and free fluorine and copper ions of tungsten, molybdenum, silicon, magnesium, vanadium, zirconium, silver, By weight based on the total weight of the emulsion-type water-soluble cutting oil composition. The method according to claim 1,
Wherein the content of one or more metal ion metal ions selected from tungsten, molybdenum, silicon, magnesium, vanadium, zirconium, silver, titanium and hafnium is 10 to 5,000 ppm. The method according to claim 1,
A water-soluble cutting oil composition of emulsion type, wherein a free fluorine content is added in an amount of 5 to 500 ppm. The method according to claim 1,
A water-soluble cutting oil composition of emulsion type, wherein 5 to 50 ppm of copper ions are added. A method for pretreating a metal surface using the emulsion type water-soluble cutting oil composition of claim 1,
Degreasing, degreasing, blanketing, degreasing, coating, washing, and pure water.


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